JP2007506968A - Sensor array integrated electrochemical chip, formation method thereof, and electrode coating - Google Patents

Abstract

【Task】
A sensor array integrated electrochemical chip having a plurality of electrodes is provided. The plurality of electrodes may be formed on a base plate coupled to a cover plate having an opening. The opening is a window or indentation. These plates are adjacent so as to form a cavity in which a plurality of electrodes are disposed. The plurality of conductive lines connecting the plurality of electrodes to the electrochemical device may be formed on the same surface as the surface of the base plate on which the electrodes are formed. At least one of the electrodes may be covered with a film doped with a ferrocene compound. This coating may be a benzoylferrocene-doped lipid bilayer. The doped ferrocene compound may be oxidized.

Description

  The present invention relates to a sensor array integrated electrochemical chip, a method for forming the chip, and electrode coating.

  Electrochemical sensors are useful for detecting the presence or measuring the concentration of a target chemical or biochemical in a fluid.

  A typical electrochemical sensor includes a detection electrode (also known as a working or measurement electrode) and one or both of a counter electrode (also known as an auxiliary electrode) and a reference electrode. During operation, these electrodes are immersed in a fluid containing the target substance. An important step in the electrochemical reaction is the movement of electrons between the working electrode surface and the molecules in the interface region (or in the fluid or immobilized on the electrode surface). When the working electrode touches the target material, an electrical signal is detected. This electrical signal is generated by a change in the potential of the electrode or the flow of current (current) through the electrode. This potential change or electron flow is generated in response to a voltage signal applied to the electrode as a result of a redox reaction known as a redox reaction occurring at the electrode surface.

  The electrode provided in the sensor may be covered with a film that controls the characteristics, selectivity, and detection sensitivity of the sensor. For example, it may be desirable to control the electrical resistance at the interface between the electrode and the fluid. Resistance at the interface affects the current response of the electrode. This is because the resistance at the interface affects the water permeability of the electrolyte that touches the electrode, and consequently the S / N ratio. In this regard, metals supported on lipid bilayers (s-BLM) have been used as coatings on the electrodes. See, for example, Tien et al., “Supported Bilayer Lipid Membranes as Ion and Molecular Probes”, Analytical Sciences, (1998), vol. 14, p. However, with the known s-BLM coating, the electrical resistance only increases to a limited extent. Furthermore, with the known s-BLM coating, the resistance of the coating material is difficult to control, and the formed coating is damaged by strict handling at the laboratory level, so it is difficult to obtain a stable specific resistance. .

  Sensor array integrated devices are useful because they are small and can be used to analyze the same component at different measurement points simultaneously or to analyze different components of a sample simultaneously. A number of techniques have been used to form electrochemical sensor array integrated devices. For example, US Pat. No. 6,315,940 of Nisch et al. Is a microelement device having a base plate and a cover plate, the cover plate having a plurality of micro cuvettes, Each of the micro cuvettes includes a detection electrode formed on the surface of the base plate or formed in a third plate sandwiched between the cover plate and the base plate. ing. However, these existing technologies have the disadvantage that the integrated device fabrication process is relatively complex.

  Therefore, there is a need to improve the method of forming the electrode and sensor array integrated electrochemical chip by improving the electrode coating.

  A sensor array integrated electrochemical chip comprising an array of electrodes is provided. At least one electrode of the array of electrodes may be coated with a coating doped with a ferrocene compound. The array of electrodes may be formed on a base plate coupled with a cover plate. The cover plate has an opening so that an array of electrodes exists in a cavity formed by the base plate and the cover plate. The plurality of conductive lines connecting the plurality of electrodes to the electrochemical device may be formed on the same surface of the base plate on which the plurality of electrodes are formed.

  According to one aspect of the present invention, there is provided a sensor array integrated electrochemical chip comprising an array of electrodes, wherein at least one electrode of the array of electrodes is coated with a film doped with a ferrocene compound. .

  According to another aspect of the invention, a first plate forming step of forming a first plate by depositing a conductive layer on a first support and etching the conductive layer to form an array of electrodes; Etching the opening of the second support so that the first plate and the second plate form a second plate forming step for forming the second plate, and a cavity in which the array of electrodes is disposed. And a bonding step of bonding the second plate to the first plate. The opening may be a window or a depression. The method may further comprise a coating step of coating at least one electrode of the array of electrodes with a coating doped with a ferrocene compound. This method may further comprise an oxidation step of oxidizing the ferrocene compound.

  According to still another aspect of the present invention, the method includes a metal array forming step of forming a metal array, and a coating step of coating at least some elements of the metal array with a lipid bilayer membrane doped with a ferrocene compound. A method of forming an electrochemical chip is provided.

  According to still another aspect of the present invention, there is provided a method of using a ferrocene compound that uses a ferrocene compound as a dopant in an electrode coating.

  According to yet another aspect of the present invention, a first plate having an array of electrodes and a cavity having an opening and in which the array of electrodes is disposed are formed together with the first plate. A sensor array integrated electrochemical chip comprising a second plate coupled to one plate is provided. The opening may be a window or a depression. A plurality of first plates extending on the same surface of the first plate on which the array of electrodes is formed, each extending outward from one electrode of the array of multiple electrodes beyond the periphery of the array of electrodes; A conductive wire may be provided.

  Other aspects, features and advantages of the present invention will become apparent to those skilled in the art when considering the following description of specific embodiments of the invention in conjunction with the accompanying drawings.

When used here,
● “Electrode array” means at least two electrodes formed in an arbitrary pattern. These electrodes may be interconnected or wired independently.

  ● “Sensor array” means an array of sensors consisting of the same or different sensors.

  ● “Coupled” means held together chemically or mechanically or otherwise.

● “Ferrocene compound” means a chemical compound containing a ferrocene group. Ferrocene group has the formula _{C 5 H 5 FeC 5 H 4} - have the. Examples of ferrocene compounds include ferrocene _{(C 5 H 5 FeC 5 H} 5) and benzoyl ferrocene _{(C 5 H 5 FeC 5 H} 4 COC 6 H 5).

  In summary, a sensor array integrated electrochemical chip may include an electrode array. At least one electrode of the array of electrodes may be coated with a coating doped with a ferrocene compound, such as a lipid bilayer (s-BLM) doped with benzoylferrocene. These electrodes may be formed on the base plate. The base plate may be coupled to the cover plate. The base plate has an opening so that an array of electrodes is disposed in a cavity formed by the base plate and the cover plate. The opening of the cover plate may be a window or a recess. These electrodes may be interconnected or wired independently. The electrode and the connecting line may be formed on the same surface of the base plate.

  The ferrocene-doped film has a high electric resistance. Thus, the resistance of an electrode coated with a ferrocene-doped coating is high compared to the electrical resistance of an uncoated electrode or an electrode coated with a conventional undoped s-BLM. The increase in the electrode resistance of the coating covering the electrode can be controlled by the doping concentration and the degree of oxidation of the ferrocene compound. In this regard, it has been found that oxidation of doped ferrocene compounds increases resistance. For appropriate resistance, the S / N ratio of the sensor can be increased.

  1 and 2 schematically show an electrochemical chip 10 including a base plate 12 and a cover plate 14. An array of a plurality of electrodes 16 is formed on the base plate 12. The cover plate 14 has an opening or window 17. Base plate 12 and cover plate 14 together define a cavity or reaction chamber 18 such that an array of electrodes 16 is within reaction chamber 18.

  Optionally, one or more cantilevers 20 can be provided on the cover plate 14 as a support for external electrodes (not shown) such as at least one of the external counter and reference electrodes. Each external electrode may be inserted into the opening 22 of the cantilever 20 and extended to the reaction chamber 18.

  The electrodes 16 may all be working electrodes. Alternatively, at least one of one or more counter electrodes and one or more reference electrodes may be included. Each electrode 16 may be individually electrically controlled through a plurality of contact holes 24 on a printed wiring board (PCB) 26. The PCB 26 provides an electrical input / output connection to at least one of an external electrical device and an electronic device. As will be appreciated by those skilled in the art, bonding pads and conductive wires (also known as “runners”) are typically used to connect the electrodes to the contact holes 24. The external device may be connected to the electrode through the contact hole 24. Alternatively, the bonding pad and the conductive line may directly connect the electrode to an external device. Bonding pads and conductive lines can also be formed on the base plate 12. However, for the sake of clarity, the bonding pads and conductive lines connecting the electrodes 16 to the contact holes 24 are not shown in FIG. 1 (however, they are shown in FIG. 7).

  Electrochemical chip 10 may be of various sizes and shapes suitable for a particular application. For example, the electrochemical chip 10 may be a chip size that varies between 1 × 1 cm and 2 × 2.25 cm, and includes a chamber area that varies between 6 × 6 mm and 2 × 44 mm.

Although an array of 5 × 5 patterned electrodes is shown in FIG. 1, the array of electrodes 16 may have any suitable electrode pattern or number of electrodes, depending on the application. The electrode 16 may have various shapes such as a square, a rectangle, a circle, and an oval. Also, the electrode 16 can be of various sizes and can be made very small such that its length and width are smaller than 90 μm. Testing these diameters from 10 μm to 90 μm has shown that these sizes are suitable. Typically, each working electrode may have a surface area of 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ cm ² or less. In biochemical applications, the smaller the size, the better. The electrodes 16 are spaced uniformly or non-uniformly at various inter-electrode distances depending on the application. For example, an interelectrode distance in the range of 10 to 100 μm has been found to be suitable for an exemplary electrochemical chip. The pixel size of the chip 10 may also be different. A 0.25 mm long pixel has been found suitable for a typical electrochemical chip.

  As shown in FIG. 2, the base plate 12 may be coupled to the cover plate 14 by a coupling material 38.

  The base plate 12 includes a base wafer 30, a first insulating layer 32, a conductive layer 34, and a second insulating layer 36. The base wafer 30 may be made of silicon or other suitable material such as glass, plastic, polymer sheet, ceramic and semiconductor material. The first insulating layer 32 and the second insulating layer 36 may be made of the same material, or may be made of different materials. Suitable materials for the first insulating layer 32 and the second insulating layer 36 include silicon dioxide, silicon nitride, and other suitable organic and inorganic materials. For use in biochemical applications, the exposed material (wafer 44 and the uncovered portions of first and second insulating layers 32 and 36) can be used to form the desired electrolyte and biological materials. Should be compatible with test solution or biochemical test solution. The first insulating layer 32 and the second insulating layer 36 should be thick enough to be sufficiently insulated. Each of the first insulating layer 32 and the second insulating layer 36 may have a thickness of 0.1 to 5 μm. The conductive layer 34 may be made of a suitable conductive material such as Cr, Au, and Ti, and may itself be layered. For example, the conductive layer 34 may be formed by providing an Au layer on a Cr or Ti layer. The electrode array 16 is formed from a conductive layer 34. Conductive lines for connecting the electrodes described above to an external device may also be formed from the conductive layer 34. At least one electrode 16 may be coated with a coating 28 doped with a ferrocene compound, such as a lipid bilayer (s-BLM) doped with benzoylferrocene. If necessary, some or all of the plurality of electrodes 16 may be coated with a ferrocene-doped coating.

  Cover plate 14 includes a wafer 44 and mask layers 40, 42, 46 and 48. Wafer 44, like wafer 30, may be made of silicon or other suitable material. Mask layers 40, 42, 46 and 48 are deposited on the wafer 44 to mask the wafer 44 during etching. If the wafer 44 is to be etched by wet chemical methods, two mask layers may be deposited on both sides of the wafer 44 as shown in FIG. Inner mask layers 42 and 46 may be thermal oxide layers and outer mask layers 40 and 48 may be silicon nitride layers deposited by low pressure CVD. Mask layers 42 and 46 may be 0.03 to 1 μm thick. Mask layers 40 and 48 may be 0.1 to 2 μm thick. If the wafer 44 is to be etched by dry chemistry, it is sufficient to have a single mask layer on each side. This single mask layer may be formed of a material such as photoresist, silicon oxide, silicon nitride and other materials suitable for dry etching. One or more mask layers 40, 42, 46 and 48 may be removed after etching. However, in order to simplify the processing process, the mask layer may be held as it is.

  Examples of techniques for forming the base plate 12 and the cover plate 14 are shown in FIGS. 3A to 3C and FIGS. 4A to 4D.

  Referring to FIG. 3A, a first insulating layer 32 is deposited on a silicon wafer 30 to form a support. Next, a conductive layer 34 is deposited on the first insulating layer 32. Any suitable vapor deposition technique can be used.

  Referring to FIG. 3B, the conductive layer 34 is then patterned and etched to form the electrode array 16, a plurality of bonding pads, and circuit lines that connect each electrode to one bonding pad. Standard semiconductor micromachining techniques such as lithography techniques may be used.

  Referring to FIG. 3C, a second insulating layer 36 is then deposited on the conductive layer 34. Next, the second insulating layer 36 is etched to expose the electrode array 16 and the bonding pads. The second insulating layer 36 is not removed by etching in the region near the periphery of the electrode array 16 where the two plates to be joined contact. As shown in FIG. 2, the cover plate 14 is bonded to the base plate 12 by the remaining insulating layer 36 that is in contact with the cover plate 14.

  Referring to FIG. 4A, mask layers 42 and 46 and then mask layers 40 and 48 are sequentially deposited on both sides of the wafer 44 to form a support for forming the cover plate 14. Wafer 44 may be made of silicon. The insulating layer may be formed by a low pressure CVD technique.

  Referring to FIG. 4B, using standard semiconductor microfabrication techniques such as lithography techniques, from mask layers 40, 42, 46 and 48, a window area for reaction chamber 18, an area for bonding pads, and a cantilever 20 These areas are removed by etching, and the wafer 44 is exposed in these areas.

  Referring to FIG. 4C, the wafer 44 is etched from the front side (upper side in the drawing) facing away from the base plate 12 when the cover plate 14 is coupled to the base plate 12. Within the open region, the wafer 44 may be etched to a thickness greater than 10 μm. Referring to FIG. 4D, next, the wafer 44 is etched from the back side (the bottom side in the figure) facing the base plate 12 when the cover plate 14 is bonded to the base plate 12. Etching may also be performed on the outer side of the side surface of the wafer 44 to expose the bonding pads. To etch the wafer 44, techniques such as KOH wet chemical etching or silicon dry etching may be used.

  As described above, one or more mask layers 40, 42, 46 and 48 may be removed after etching.

  Returning to FIG. 2, the cover plate 14 is then used using techniques such as taught by Chen et al., US Pat. No. 6,503,847 (“Chen”), issued January 7, 2003. The base plate 12 and the cover plate 14 can be combined with the window 17 on the upper side of the electrode array 16. The contents of this US patent are incorporated herein by reference. In particular, a diluted polydimethylsiloxane (PDMS) solution may be used as taught by Chen. Next, the surface of the mask layer 40 (or the back side of the wafer 44 when the mask layers 40 and 42 are removed) is spin-coated with PDMS. The PDMS coating may have a thickness of 1 to 400 μm. During the coating process, the front side of the wafer 44 may be laminated with a polymer film to prevent it from being coated with PDMS. After pre-curing the PDMS until it is semi-cured, the cover plate 14 may be aligned with the base plate 12 and pressed against each other until the PDMS is fully cured. As can be seen, although not shown in FIG. 2 (for clarity), the rear side of the cover plate 14 and the inner surface of the window 17 are coated with a PDMS layer after bonding. Conveniently, since the PDMS layer is a biocompatible material, the chip 10 will be biocompatible even if the wafer 30 and the mask layer are not biocompatible.

  As can be appreciated, multiple pairs of base plates and cover plates can be formed simultaneously from two wafers. In the case of forming a plurality of pairs, the individual pairs can be separated after the PDMS is completely cured by dicing or the like. Each pair may then be wire bonded to the PCB.

  As described above, one or more electrodes 16 are covered with a ferrocene compound-doped film such as s-BLM doped with benzoylferrocene. The coating may be deposited on the electrode 16 using various methods. A typical procedure for coating electrode 16 with s-BLM doped with benzoylferrocene is as follows.

  Benzoylferrocene and dimyristoyl L-α-phosphatidylcholine (DMPC) are dissolved in analytical chloroform to make a lipid solution in which the concentration of benzoylferrocene and DMPC is in the range of 0.1 to 10 mg / ml. For example, the respective concentrations may be 1 mg / ml and 2 mg / ml.

  The electrochemical chip 10 is cleaned. For example, the chip 10 is sonicated continuously for 5 minutes in alcohol and deionized water, and then the chip 10 is air-dried.

  Apply a small amount of lipid solution to the electrode surface, for example, by dropping 20 μl of the lipid solution with a microsyringe.

  Chloroform on the electrode is gradually evaporated in air at room temperature.

1 ml of phosphate buffer (PBS) is transferred onto the electrode 16 coated with lipid. However, the phosphate buffer contains 8 g / l NaCl, 0.2 g / l KCl, 1.44 g / l Na ₂ HPO ₄ , and 0.24 g / l KH ₂ PO ₄ , and has a pH value of 7.4. is there. The phosphate buffer may be any suitable neutral aqueous solution that stabilizes the lipid bilayer.

  Other suitable doping processes such as absorption doping and diffusion doping may be employed. However, it will be appreciated that the doping process should not adversely affect the properties of the s-BLM.

  As can be seen, benzoylferrocene-doped s-BLM will spontaneously form (by molecular self-assembly) in PBS solution on the electrode.

  Experiments have shown that the electrical resistance of the s-BLM film is higher when doped with benzoylferrocene than when undoped. It has also been found that the electrical resistance can be further increased by oxidizing the doped benzoylferrocene.

When the electrode 16 is immersed in an electrolyte solution such as PBS containing potassium ferricyanide (K ₃ [Fe (CN) ₆ ]) that causes a reduction reaction on the film, for example, from −0.3 to +0.8 V When the electrode 16 receives a cyclic potential change, the benzoylferrocene in the coated s-BLM can be oxidized.

  Whether or not the benzoylferrocene in the film is oxidized can be easily inspected by examining the current response of the electrode to the reduction reaction. If the current response is small, it is oxidized. If the current response is large, it is not fully oxidized.

  Conveniently, the electrical resistance at electrode 16 can be controlled by controlling the degree of oxidation of benzoylferrocene in the s-BLM film. Furthermore, experiments have shown that the oxidation of benzoylferrocene is irreversible. That is, once oxidized, the benzoylferrocene remains oxidized, and thus a stable electrical resistance is produced at the electrode interface. (However, if the benzoylferrocene is not completely oxidized, the benzoylferrocene is further oxidized if the potential applied to the electrode is higher than the oxidation potential).

  The resistance of the coating can also be controlled by adjusting the dopant concentration.

Other ferrocene compounds may be used to dope the s-BLM film. For example, ferrocene _{(C 5 H 5 FeC 5 H} 5), or 1,1 '[(4,4'-bipiperidine) -1,1'-diyl di-carbonyl] - bis [1' - (methoxycarbonyl) ferrocene] May be used.

  Further, the s-BLM may be replaced with other suitable materials such as any suitable organic polymer or film that can be deformed, immobilized or self-assembled on the surface of the electrode 16 and can be doped with a ferrocene-containing compound. Advantageously, the doped lipid membrane retains its biocompatible microenvironment in the presence of the enzyme. Therefore, the sensor is suitable for biochemical applications.

  The coating may be permeable or impermeable depending on the type of detection mechanism employed. For example, a permeable coating may be used for an amperometric sensor, while an impermeable coating may be used for a resistance or impedance sensor.

  Different electrodes 16 may be coated with different coatings, such as coatings comprising different materials or similar materials having different oxidation states.

  In operation, the electrochemical chip 10 is wired to an external control device and a data capturing device via the contact hole 24. The reaction chamber 18 is filled with liquid. The electrode is biased in a manner typical of electrochemical sensors or sensor arrays so that an electrical signal can be detected to determine if a specific reduction reaction is occurring in the fluid and / or how fast it is occurring. multiply. Therefore, it is determined whether or not one or more specific target substances are present in the fluid, or the concentration of the substances. If necessary, one or both of an external counter electrode and an external reference electrode supported by the cantilever 20 may be used. All of the electrode 16 may be used as a working electrode. Alternatively, one or more of the electrodes 16 may be used as a counter electrode or a reference electrode.

  As can be appreciated, the electrochemical chip 10 is easy to process. The two plate structure facilitates formation of the electrode array 16. This is because the conductive layer 34 can be provided on a flat surface and then etched to form individual electrodes. Similarly, other metal compounds such as bonding pads and connection lines can be easily formed. The reaction chamber 18 can be widened and can be as deep as the thickness of the wafer 44. Since two wafers are used, more electronic devices may be mounted on the electrochemical chip 10 than on a single wafer chip.

  Conveniently, all electrodes, including the working electrode, counter electrode and reference electrode, can be formed of the same material on the same conductive layer 34. Nevertheless, any counter and reference electrodes made of different materials may be provided and supported by the cantilever 20.

  Since all of the electrodes 16 are installed in one reaction chamber 18, simultaneous detection or testing is possible. Thereby, the usage-amount and analysis time of a sample can be reduced. Other components of the same sample can be tested simultaneously. Alternatively, data obtained from multiple electrodes can be combined to obtain more accurate or reliable results.

  As can be appreciated, it is advantageous to form an electrochemical chip as taught herein, since the process is simple and inexpensive without coating the electrode with a coating doped with a ferrocene compound.

  The electrochemical chip 10 may be used for purposes other than electrochemical detection. For example, multiple electrodes can be used for AC or DC electrical measurements.

  Other aspects, features and benefits of the present invention not specifically described above can be understood by those skilled in the art from the description of this embodiment and the accompanying drawings.

  Many variations on the exemplary embodiments described herein are possible as will be appreciated by those skilled in the art. For example, the conductive layer 34 (and hence the plurality of electrodes 16) may be made of any suitable metal or alloy, such as Au, Pt, Ag indium tin oxide (ITO), or a conductive polymer. The binder for layer 38 can be any suitable biocompatible material and chemically resistant material.

  The base plate 12 and the cover plate 14 do not need to be chemically bonded. The base plate 12 and the cover plate 14 may be simply stacked and mechanically held so that there is no leakage from the reaction chamber 18. In that case, the bonding layer 38 may be omitted.

  Furthermore, the cover plate 14 may have a window shape different from that shown in FIGS. 2 and 4A-4D. For example, the window on the cover plate may have a shape other than a square when viewed from the front side. Furthermore, the windows on the cover plate need not be fully open. For example, FIG. 5 shows another sensor array integrated electrochemical chip 10 '. Here, a recess is formed by etching the opening of the cover plate 14 'only on one side. The cover plate 14 and the base plate 12 'are joined to form a cavity or reaction chamber 18'. Sample liquid can flow through channel 50 of cover plate 14 'into and out of reaction chamber 18'. All the back side of the cover plate 14 'and the side walls of the reaction chamber 18' may be coated with a biocompatible material 38 'such as PDMS.

  Another alternative cover plate 14 "without a cantilever is shown in FIG. The silicon wafer on the cover plate 14 ″ may be etched from the top or bottom.

  If necessary, the plurality of electrodes 16 may be formed on the side wall of the reaction chamber 18.

  As shown in FIG. 7, the electrodes 16 ′ may be interconnected in parallel and grouped into two or more groups, each group of electrodes being connected to a normal bonding pad via a plurality of connection lines 54. Good. As shown in the figure, each of the connection lines extends outward from one electrode beyond the peripheral edge of the electrode array.

  If the base plate and the cover plate are joined with a non-biocompatible binder, a layer of biocompatible and chemically inert material is added to the window in the cover plate before the layer is joined to the base plate. You may provide in the side wall. Thereby, a biocompatible inner surface can be provided in the reaction chamber.

  The present invention includes all such variations within its scope as defined by the claims.

The drawings illustrating exemplary embodiments of the invention are as follows.
It is a typical perspective view of a sensor array integrated electrochemical chip. It is a typical fragmentary sectional view of the electrochemical chip | tip of FIG. It is a figure which illustrates typically the method of forming the base plate of FIG. It is a figure which illustrates typically the method of forming the cover plate of FIG. It is a typical fragmentary sectional view of other sensor array integrated type electrochemical chips. It is a typical fragmentary sectional view of a cover plate. It is a partial top view of the electrode array on a baseplate.

Claims (30)

  A sensor array integrated electrochemical chip comprising an array of electrodes, wherein at least one of the electrodes is coated with a film doped with a ferrocene compound.   The sensor chip integrated electrochemical chip according to claim 1, wherein the coating is a lipid bilayer doped with the ferrocene compound.   The sensor array integrated electrochemical chip according to claim 2, wherein the ferrocene compound is benzoylferrocene.   The sensor chip integrated electrochemical chip according to claim 1, wherein the ferrocene compound is oxidized. A first plate comprising an array of said electrodes;
And a second plate coupled to the first plate to form a cavity with the first plate in which the array of electrodes is disposed. The sensor array integrated electrochemical chip according to claim 1.   6. The sensor array integrated electrochemical chip according to claim 5, wherein the opening is a window.   6. The sensor array integrated electrochemical chip according to claim 5, wherein the opening is a recess.   The sensor array integrated electrochemical chip according to claim 5, wherein the array of electrodes comprises an array of a plurality of working electrodes.   9. The sensor array integrated electrochemical chip according to claim 8, wherein each of the plurality of working electrodes is covered with a lipid bilayer doped with a ferrocene compound.   9. The sensor array integrated electrochemical chip according to claim 8, wherein the electrode array further comprises at least one of a counter electrode and a reference electrode.   6. The sensor array integrated electrochemical chip according to claim 5, wherein the second plate includes at least one cantilever electrode extending into the window.   12. The sensor array integrated electrochemical chip according to claim 11, wherein the at least one cantilever electrode includes at least one of a cantilever reference electrode and a cantilever counter electrode.   6. The sensor array integrated electrochemical chip according to claim 5, wherein the layer in the first plate in contact with the second plate is an insulating layer. A first plate forming step of forming a first plate by depositing a conductive layer on a first support and etching the conductive layer to form an array of electrodes;
A second plate forming step of forming a second plate by etching the opening of the second support;
A coupling step of coupling the second plate to the first plate such that the first plate and the second plate form a cavity in which the array of electrodes is disposed. Chemical chip formation method.   The method of forming an electrochemical chip according to claim 14, wherein the opening is a window.   15. The method of forming an electrochemical chip according to claim 14, wherein the opening is a depression.   The method of forming an electrochemical chip according to claim 14, further comprising a coating step of coating at least one electrode of the array of electrodes with a coating doped with a ferrocene compound.   The method for forming an electrochemical chip according to claim 17, further comprising an oxidation step of oxidizing the ferrocene compound.   15. The method of forming an electrochemical chip according to claim 14, wherein the coating is a lipid bilayer doped with the ferrocene compound.   The method for forming an electrochemical chip according to claim 14, wherein the ferrocene compound is benzoylferrocene.   And further comprising an etching step of etching the conductive layer to form a plurality of conductive lines each extending outwardly from one electrode of the electrode array beyond the periphery of the electrode array. 15. The method for forming an electrochemical chip according to claim 14,   The method for forming an electrochemical chip according to claim 14, further comprising a first support forming step of forming the first support by depositing an insulating layer on a silicon wafer. A vapor deposition step of vapor-depositing an insulating layer covering the conductive layer around the periphery of the electrode array;
The method according to claim 22, wherein the second plate is bonded to the first plate with an insulating layer covering the conductive layer.   The method of claim 14, wherein the second support comprises a silicon wafer. A metal array forming step of forming a metal array;
A coating step of coating at least some elements of the metal array with a lipid bilayer doped with a ferrocene compound;
A method of forming an electrochemical chip comprising the steps of:   Use of a ferrocene compound using a ferrocene compound as a dopant in an electrode coating. A first plate comprising an array of electrodes;
And a second plate coupled to the first plate so as to form a cavity in which the plurality of electrodes are disposed together with the first plate. Array integrated electrochemical chip.   28. The sensor array integrated electrochemical chip according to claim 27, wherein the opening is a window.   28. The sensor chip integrated electrochemical chip according to claim 27, wherein the opening is a recess. The first plate extends outwardly from one electrode of the electrode array beyond the periphery of the electrode array on the same surface of the first plate on which the array of electrodes is formed. 28. The sensor chip integrated electrochemical chip according to claim 27, comprising a plurality of conductive lines.

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